1. Field of the Invention
This invention relates to urease inhibited urea based fertilizer compositions. More particularly, this invention relates to urease inhibited urea based fertilizer compositions which contain certain diaminophosphinyl compounds containing oxidized sulfur functions, as the urease inhibitors, and to methods and compositions for inhibiting the action of soil urease through use of such compounds.
2. The Prior Art
It is well known in the art to use urea and urea compositions in fertilizers, for application to the soil. The effective life of such fertilizers, however, is of short duration wherever microbiological activity exists in the soil to which the fertilizer is applied. This is due to the fact that urea is hydrolyzed rapidly, and nitrogen is lost in the form of ammonia, when urea is placed under or on the surface of soil which contains urease. Urease, a crystallizable enzyme occurring in numerous bacteria and fungi, as for example Micrococcus urease, catalyzes the conversion of urea into ammonia and carbon dioxide. The reactions are as follows:
CO(NH.sub.2).sub.2 +2H.sub.2 O Urease 2NH.sub.3 +H.sub.2 CO.sub.3 PA1 NH.sub.3 +H.sub.2 O NH.sub.4.sup.+ +OH.sup.- PA1 R.sub.1 is ##STR2## wherein: R.sub.1 ' is amino or substituted or unsubstituted alkyl, aryl wherein permissible substituents are selected from the group consisting of one or more alkyl, aryl, halogen, trihalomethyl, nitro, cyano, alkanoyl, alkylcarboxylate, arylcarboxylate, alkoxy, hydroxy, alkylmercapto, arylmercapto, mercapto, amino, alkylamino, dialkylamino, arylamino, diarylamino, diaminophosphinyl, N-diaminophosphinyl, O-diaminophosphinyl, S-diaminophosphinyl, carbamoyl and carbamoyldiaminophosphinyl groups; PA1 R.sub.2 is hydrogen, or substituted or unsubstituted alkyl or aryl wherein permissible substituents are as in R.sub.1 ' above; and PA1 R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are the same or different and are hydrogen or alkyl having from about 1 to about 4 carbon atoms. PA1 R.sub.1 is ##STR4## wherein R.sub.1 ' is amino or substituted or unsubstituted alkyl, aryl wherein permissible substituents are selected from the group consisting of one or more alkyl, aryl, halogen, trihalomethyl, nitro, cyano, alkanoyl, alkylcarboxylate, arylcarboxylate, alkoxy, hydroxy, alkylmercapto, arylmercapto, mercapto, amino, alkylamino, dialkylamino, arylamino, diarylamino, diaminophosphinyl, N-diaminophosphinyl, O-diaminophosphinyl, S-diaminophosphinyl, carbamoyl and carbamoyldiaminophosphinyl groups; PA1 R.sub.2 is hydrogen, or substituted or unsubstituted alkyl or aryl where permissible substituents are as in R.sub.1 above; and PA1 R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are the same or different and are hydrogen or alkyl having from about 1 to about 4 carbon atoms. PA1 X is oxygen; PA1 R.sub.1 is ##STR5## wherein: R.sub.1 ' is alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl; PA1 R.sub.2 is hydrogen, or R.sub.1 '; and PA1 R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are hydrogen. PA1 X is oxygen; PA1 R.sub.1 is ##STR6## wherein R.sub.1 ' is alkyl having from about 1 to 7 carbon atoms, phenyl, or phenylalkyl or alkylphenyl having from about 7 to about 12 carbon atoms; PA1 R.sub.2 is hydrogen or R.sub.1 ; and PA1 R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are hydrogen.
A portion of the ammonia thus formed is held by absorbing constituents of the soil and is available to plants as nutrient. However, a large amount of the ammonia may be lost to the air. A further problem resulting from the action of urease is the accumulation of ammonium in the soil which can damage germinating seedlings and young plants.
One approach to the reduction of problems resulting from the activity of soil urease toward soil applied urea is to find compounds that inhibit urease activity when applied to soils in conjunction with fertilizer urea. This approach has received considerable attention, and several classes of compounds have been used as urease inhibitors.
For example, certain prior art describes various phosphoro compounds which are useful as urease inhibitors. Illustrative of such prior art are East German Patent Nos. 142,714; 212,026; 122,177; 122,621 and 130,936, and Great Britain Patent No. 1,494,774 which describe various phosphorodiamidate compounds as urease inhibitors. Also exemplary of such prior art is U.S. Pat. No. 4,242,325 which describes a method of controlling the enzymatic decomposition of urea to ammonia and carbonic acid due to the action of urease which comprises exposing the enzyme to certain phosphoric triamide compounds. U.S. Pat. No. 4,182,881 describes the use of certain N-[diaminophosphinyl]arylcarboxyamide compounds as inhibitors of the enzyme urease in the urinary tract. U.S. Pat. No. 4,225,526 describes the use of 8-[(4-aminophenyl)sulfonyl]amino-2-naphthalenyl phosphorodiamidate compounds as inhibitors of the enzyme urease, and U.S. Pat. No. 4,222,948 describes the use of ([(4-aminophenyl)sulfonyl]amino)phenyl phosphorodiamidates as inhibitors of the enzyme urease. Nakanishi, M, and Oe, T, Japan Patent No. 7379; Chem. Asbtr. 1967, 67, 81947X describes certain diaminophosphinyl compounds containing oxidized sulfur functions and discloses that such compounds are useful in treating diabetes mellitus.